TWI374155B - - Google Patents

Description

丄374155

IX. Description of the Invention: [Technical Field to which the Sun and the Moon belong] The present invention relates to a color-sensitive photosensitive composition, and more particularly to a colored photosensitive composition which can be used for forming a light-shielding film, which is used for color filter Among the black matrix of the light sheet. [Prior Art] Conventionally, as a method of producing a color filter using a pigment, there have been a dyeing method, an electrodeposition method, an inkjet method, a pigment dispersion method, and the like. In the case of the pigment dispersion method, a photosensitive resin obtained by dispersing a pigment by a dispersant or the like is added with a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc., to obtain a photosensitive coloring. The resin composition is applied onto a soil substrate, dried, and then exposed and developed to form a color pattern. Thereafter, heating is performed to fix the pattern to form a pixel. These steps are repeated for the colors to form a color filter. The photosensitive coloring grease composition for forming an image of such a color filter is required to have sufficient analytical properties and adhesion to a substrate and a small amount of development residue. Moreover, in the case of the pigment dispersion method, it is required to supply to the photolithography step, so the industry has been striving that no residue or segregation is generated in the removed portion of the development step; the removed portion has sufficient solubility; (edge) clarity and other pixel formation. Further, in recent years, as the size of the substrate to be used has increased, the development degree (marg i η ) has been required to be large. In particular, as in the case of black matrices, it is required to cover the whole wavelength region of light. It is known to be separated. Each tree is dissolved in the light. 5 1374155

In the case of ability, it is very difficult to set the difference in the crosslink density between the exposed portion and the unexposed portion. Therefore, even in the exposed portion, the side of the light-emitting surface is sufficiently hardened, but it is not cured on the side of the base surface. Further, since a large amount of black coloring material which is insoluble in the developer is blended, there is a problem that developability is remarkably lowered. Therefore, in order to solve such a problem, a photosensitive colored resin composition using a novolac epoxy acrylate as a binder has been disclosed (for example, refer to Patent Document 1 and discloses that it has a use A reaction product of a carboxyl group-containing acrylic resin and an aliphatic epoxy group-containing unsaturated compound is used as a binder resin composition (for example, see Patent Document 2). Further, an acid anhydride is provided, and two epoxy resins are contained. A resin composition of a polyvalent carboxylic acid obtained by reacting a reaction product of a compound with a monocarboxylic acid (see Patent Document 3). [Patent Document 1] Japanese Patent Laid-Open No. Hei No. 84 1-26 [Patent Document 2] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-43573. [The present invention] The resin composition disclosed in the above Patent Documents 1 to 3 is insufficient in sensitivity, has poor fineness and is easily peeled off, and remains in the residue. And other issues. Further, since the development margin is small, there is a problem that the shadow is peeled off to the exposed portion, and the edge of the pattern is not flat. In view of the above-mentioned problems, the present invention has an object of providing a color-sensitive photosensitive composition which has sufficient sensitivity, good fineness, and can form a pattern excellent in contour shape. . In the line

[Means for Solving the Problem] The present inventors have found that the present invention has been accomplished by solving the above problems in order to solve the above problems, and the present invention has been completed by the following coloring photosensitive composition, and the colored photosensitive composition is contained therein. A resin (A1) obtained by reacting a specific compound epoxy compound (al) with a reaction product containing an ethylenically unsaturated acid compound (a-2) and further with a polybasic acid anhydride (a-3). More specifically, the present invention provides a coloring photosensitive composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a component (C), characterized in that the photopolymerizable compound (A) a resin (A1) obtained by reacting an epoxy compound (al) with a carboxylated (a-2) group containing an ethylenically unsaturated group, and further with a polybasic acid anhydride (a-3); Al) an epoxy compound having a biphenyl skeleton and a Cardo skeleton. Research. In the present invention, a resin having a different skeleton can be used to prepare a pattern having excellent linearity by sensitivity by blending a resin having a different skeleton. Further, it is possible to easily form no peeling or residue on the board, and it does not form an undercut shape during development, and a good black matrix pattern excellent in contour shape is not damaged in the substrate. 1374155

Since the undercut shape is not formed at the time of development, it is possible to easily provide a color filter for a liquid crystal display having a fine line adhesion of 10 or less and a high contrast ratio and excellent color development of R, G, and B. In addition, when the concentration of the coloring material is high, a photosensitive coloring resin composition for a color filter excellent in image formation property, a color filter using the photosensitive colored resin composition, and a liquid crystal display device can be provided. . Further, by combining a specific binder resin and a dispersion enthalpy, it is possible to provide a color-lighting photosensitive photosensitive resin composition excellent in sensitivity and solubility balance, and excellent in sharpness and adhesion of pixel edges. . [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. The colored photosensitive composition of the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), and a color former (C). <Photopolymerizable Compound (A) > The photopolymerizable compound (A) is a material which is subjected to φ polymerization by irradiation with light such as ultraviolet rays to be cured. Specifically, the photopolymerizable compound (A) contains a reaction product of an epoxy compound (a-fluorene) and a phthalic acid compound (a-2) containing an ethylenically unsaturated group, and further with a polybasic acid anhydride (a-3). The resin (Α1) β-pyrimidal' epoxy compound (a_1) obtained by the reaction contains an epoxy compound having a biphenyl skeleton and an epoxy compound having a cockroach (Cardo) skeleton. • The above resin (A1) can be used in the following two aspects. In the first aspect '• Resin (A1) contains: by having (a-Ι) a component having biphenyl bone 8 (S) 1374155

a resin obtained by reacting an epoxy compound with a component (a-2), and further a component (Α1-1): and an epoxy compound having an anthracene skeleton of 4 components and (a- 2) a resin obtained by reacting with a component (a-3), in other words, the resin (A1) contains a resin (A1) and a resin (a resin mixture, the resin (A1-1) contains a biphenyl a unit derived from a base oxygen compound, and the resin (A1-2) contains a unit derived from an epoxy compound of an anthracene skeleton. Further, in the second aspect, the resin (A1) contains: (a-1) component The resin (A1-3) obtained by reacting an epoxy compound having a biphenyl skeleton and a reactant of the epoxy compound and the component (a-2), and further reacting the four components. In other words, the resin (A1) is contained. -3), the resin (A3) contains a unit derived from a bonded epoxy compound, and a unit derived from an anthracene skeleton. The above epoxy compound having a biphenyl skeleton (a) -1) The unit is better than the amount derived from the epoxy compound with a noisy skeleton. 1: 99 to 80: 20, more preferably 5: 95~ by the epoxy compound (a-1) having a biphenyl skeleton derived from a unit derived from an epoxy compound having an anthracene skeleton Within this range, the linearity of the pattern and the contour after development can be made good. [Epoxy compound (a-Ι)] The epoxy compound (a-1) used in the present invention has % (a-3). Bu is the reaction of (a-1) (A Bu 2) » A1-2) The ring of the skeleton consists of a phenyl skeleton with a sputum as a % (a-3) ΐ lipid (A1) The mass of the unit derived from oxidation is 30: 70. The unit mass ratio of the twin is more than that of the epoxy compound of the biphenyl bone 9 1374155 and the epoxy compound having an anthracene skeleton. [Epoxy compound having a biphenyl skeleton] An epoxy compound having a biphenyl skeleton, having one or more biphenyl skeletons represented by the following chemical formula (4) in the main chain, and having one or more rings Oxygen. The epoxy compound (a-1) is preferably one having two or more epoxy groups, and the epoxy compound (a-fluorene) may be used singly or in combination of two or more. [Chemical 1]

In the formula (4), a plurality of R1's are each independently, and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent, and 1 represents a number of 1 to 4. Among the epoxy compounds having a biphenyl skeleton, an epoxy compound represented by the following formula (1) is preferably used, and an epoxy compound represented by the following formula (2) is particularly preferably used. By using the epoxy compound of the formula (2), it is possible to provide a color-sensitive photosensitive composition which is excellent in balance between sensitivity and solubility, and which is excellent in clarity and adhesion of the pixel edge. [Chemical 2]

In the formula (1), a plurality of R1's are each independently represent a hydrogen atom, an alkyl group having 10 1374155 or 1 to 12 carbon atoms, a self-priming atom or a phenyl group which may have a substituent, and η represents an integer of 1 to 4. m is an average value and represents a number from 0 to 10, preferably less than one. 〕

[In the formula (2), m is an average value, and represents a number of 0 to 10, preferably less than 1. Further, among the epoxy compounds having a biphenyl skeleton, an epoxy compound represented by the following formula (5) is preferably used. By using the epoxy compound of the formula (5), it is possible to provide a color-sensitive photosensitive composition which is excellent in balance between sensitivity and solubility, and which is excellent in sharpness and adhesion of the edge of the pixel.

[Chemical 4]

In the formula (5), a plurality of R3's are each independently, and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a dentate atom, or a phenyl group which may have a substituent. m is an average value representing a number from 0 to 10, preferably less than one. [Epoxy compound having an anthracene skeleton] The epoxy compound having an anthracene skeleton is a compound having two epoxy groups in the anthracene skeleton, and specifically, it is preferably the following chemical formula (3) (S) ) 11 1374155 represents the compound. (3) An epoxy compound having an anthracene skeleton represented by the formula (3),

It has a scent structure and is therefore highly resistant to heat and chemicals. Therefore, by blending an epoxy compound having an anthracene skeleton, the heat resistance and chemical resistance of the coloring photosensitive composition can be improved. [Carboxylic acid compound (a-2) containing an ethylenically unsaturated group]

The carboxylic acid compound (a-2) having an ethylenically unsaturated group is preferably a monocarboxylic acid compound containing a reactive ethylenic double bond such as a propenyl group or a methacryl group in the molecule. Examples of the ethylenically unsaturated group-containing carboxylic acid compound (a-2) include acrylic acid, methacrylic acid, /3-styrylacrylic acid, /5-mercaptoacrylic acid, and α-cyanocinnamic acid. Cinnamon acid and so on. The carboxylic acid compound (a-2) containing an ethylenically unsaturated group may be used singly or in combination of two or more. As a method of reacting the above epoxy compound (a-fluorene) with the ethylenically unsaturated group-containing carboxylic acid compound (a-2), a conventionally known method can be used. For example, the following methods may be mentioned: a tertiary amine such as triethylamine or benzylethylamine, dodecyltrimethylammonium hydride, tetradecyl ammonium hydride, tetraethylammonium hydride, or benzyl group. a quaternary ammonium salt such as triethylammonium vaporate, pyridine or triphenylphosphine as a catalyst, and an epoxy compound (a-fluorene) and an ethylenically unsaturated group 12 1374155 carboxylic acid compound (a-2) , reacting in an organic solvent at a reaction temperature of 50 to 150 ° C for several hours to several tens of hours. The epoxy compound (a-fluorene) and the ethylenic acid compound (a-2) containing an ethylenically unsaturated group. The ratio of the amount used in the reaction is usually 1:0, based on the ratio of the epoxy equivalent of the epoxy compound (a-1) to the carboxylic acid equivalent of the ethylenically unsaturated group-containing carboxylic acid compound (a-2). 5 to 1:2, preferably 1:0.8 to 1:1.25, more preferably 1:1. When the ratio of the epoxy equivalent of the epoxy compound (a-fluorene) to the carboxylic acid equivalent of the ethylenically unsaturated group-containing carboxylic acid compound (a-2) is within the above range, there is a tendency to improve the crosslinking efficiency. Therefore, it is better. [Polyhydric anhydride (a-3)] As the polybasic acid anhydride (a-3), a compound containing an acid anhydride which is a carboxylic acid having two or more carboxyl groups and having at least two benzene rings can be used. Examples of the polybasic acid anhydride (a-3) include an acid anhydride having a biphenyl skeleton represented by the following formula (6), and an organic group bonded to two benzene rings represented by the following formula (7). Anhydride.

〇 II

[Chem. 6] 〇 II 0:

H ; 〇 , c

II 0

(S) 13 1374155 [In the formula (7), R4 represents an exudation group which may have a substituent having 1 to 10 carbon atoms. At least two benzene rings can be introduced into the photopolymerizable compound (A) by using the acid anhydride of the carboxylic acid having two or more carboxyl groups.

Further, the polybasic acid anhydride (a-3) may contain other polybasic acid anhydrides in addition to the above-mentioned acid anhydride having at least two benzene rings. Examples of the other polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and mercaptohexahydroorthophenylene. Dicarboxylic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyrogallic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-mercapto Hexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-mercaptotetrahydrophthalic acid Anhydride, 4-nonyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride. These polybasic acid anhydrides may be used singly or in combination of two or more.

As a method of reacting the epoxy compound (a-1) with the ethylenically unsaturated group-containing carboxylic acid compound (a-2) and further reacting with the polybasic acid anhydride (a-3), previously known ones can be used. method. Further, the molar number of the OH group in the reaction of the epoxy compound (a-1) and the ethylenically unsaturated group-containing carboxylic acid compound (a-2), and the acid anhydride group of the polybasic acid anhydride (a-3) The ratio of the equivalent ratio is usually 1:1 to 1:0.1, preferably 1:0.8-1:0.2. By the molar number of the OH group in the reaction of the epoxy compound (a-1) with the ethylenically unsaturated group-containing carboxylic acid compound (a-2) and the anhydride group of the polybasic acid anhydride (a-3) The equivalence ratio is set within the above range, so that

(S 14 1374155

The solubility in the developer tends to be moderate, which is preferable. The acid value of the resin (A1) obtained by reacting the epoxy compound (al) with the compound (a-2) containing the ethylenically unsaturated group, and further with the polybasic acid anhydride (a-3), The resin solid content is preferably from 10 to 150 mgKOH/g, more preferably from 70 to 110 mgKOH/g. When the acid value of the fat (A1) is 10 mgKOH/g or more, sufficient solubility in development can be obtained. Further, by setting the acid value of the resin (A1) to not more than mgKOH/g, sufficient curability can be obtained and surface properties can be improved. Further, the weight average molecular weight of the resin (A1) is preferably from 1 to 15,000, more preferably from 2,000 to 1,3,000. By setting the weight average molecular weight of the resin to 1,000 or more, heat resistance and degree can be improved. Further, by setting the weight average molecular weight of the resin (A1) to 15 or less, sufficient liquid can be obtained in the developer. Solubility. [The monomer containing an ethylenically unsaturated group] The photopolymerizable compound (A) used in the invention is preferably a monomer having an ethylenically unsaturated group. Monofunctional monomers and polyfunctional monomers, and examples of the monofunctional monomer include acrylamide, hydroxymethyl (meth) acrylamide, methoxy fluorenyl propylene amide, ethoxy fluorenyl (fluorenyl) acrylamide, propoxy decyl acrylamide, butoxy methoxymethyl (mercapto) acrylamide, hydrazine-hydroxy (meth) acrylamide, hydrazine-hydroxymethyl ( Methyl) acrylamide' (曱J enoic acid, fumaric acid, maleic acid, maleic anhydride, Ikonic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2 - In the case of propylene, the carboxylic acid is reversed by 150 in the sap, 000 Α 1 ). The film is strong, 000 contains, and has: (methyl) group. Sulfhydryl :) propionic acid, 15 : _ 2 - 1374155 tri ester acetate sulfonate XI / propyl > base U 曱

, - 2 匕曰S · Rare Earth Formate) 3⁄4 propyl. Methyl C曱, '(ii acid butyl sulfonate) 3⁄4 alkenyl propyl methyl C ethyl hexyl ester, (fluorenyl) acrylate ring Hexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxy (meth) acrylate Propyl ester, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, (indenyl) methacrylate, dimethyl (meth) acrylate Glycosyl ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, ortho-benzene A (meth)acrylic acid half ester of a dicarboxylic acid derivative or the like. These monofunctional monomers may be used singly or in combination of two or more. On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Mercapto) acrylate, polypropylene glycol di(meth) acrylate, butanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(曱) Acrylate, trihydroxymercaptopropane tri(meth)acrylate, glycerol di(decyl)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , pentaerythritol bis(indenyl) acrylate, pentaerythritol tri(indenyl) acrylate, pentaerythritol tetrakis(meth) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexa(meth) acrylate, 2, 2-bis(4-(indenyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(indolyl)propenyloxypolyethoxyphenyl)propane, (A Base) 2-hydroxy- 3-(methyl) acrylate Alkenyl acyl group, propylene glycol diglycidyl 161374155

Glycerol ether di(meth)acrylate, diethylene glycol diglycidyl ether di(indenyl) acrylate, diglycidyl diglycidyl di(meth)acrylate, glycerin triacetate vinegar, glycerin Polyglycidyl poly(methyl)propene acid, ethyl urethane (meth) acrylate (ie, toluene diisocyanate), trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate Reaction of 2-hydroxyethyl methacrylate, fluorenyl bis(meth) acrylamide, (mercapto) acrylamide, methylene ether, polyol and N-hydroxymethyl (meth) propylene A polyfunctional monomer such as a condensate of guanamine or a triacryl formal or the like. These polyfunctional monomers may be used singly or in combination of two or more. The amount of the monomer containing the ethylenically unsaturated group is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, based on the solid content of the coloring photosensitive composition. When the amount of the monomer containing the ethylenically unsaturated group is within the above range with respect to the solid content of the colored photosensitive composition, the balance of sensitivity, developability, and resolution tends to be easily obtained, which is preferable. The content of the photopolymerizable compound (A) is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, based on the solid content of the coloring photosensitive composition. When the content of the photopolymerizable compound (A) is within the above range with respect to the solid content of the coloring photosensitive composition, the sensitivity, the developability, and the analytical property tend to be balanced, which is preferable. <Photopolymerization initiator (B) > As the photopolymerization initiator (B), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-b Ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propane-propanone, 1-(4-isopropylbenzene 17 1374155

2-hydroxy-2-methylpropane-buxone, di(4-dodecylphenyl)-2-hydroxy-2-mercaptopropane-buxone, 2,2-dimethoxy- 1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2- 2-methyl-l-[4-(methylthio)phenyl]-2- morphol inopropane-1-one ), 2-benzyl-2-dimethylamino-1-() 4-Morpholinyl)-butan-1-one, ethyl ketone-l-[9-ethyl-6-(2-mercaptobenzylidene)-9H-indazol-3-yl]- 1-(0-acetamidine), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 4-benzylidene-4'-mercaptodimethyl sulfide, 4-dimethyl Amino benzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-didecylaminobenzoate, butyl 4-didecylaminobenzoate, 4-dimethyl benzoate Amino-2-ethylhexyl ester, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-/5-methoxyethyl acetal, benzyl dimethyl ketal, Phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)indole, 0-phenylmercaptobenzoic acid decyl ester, 2,4-diethylthioxanthone, 2-chloro Thioxanthone, 2, 4-di Thiophenone, 1-gas-4-propoxythioxanthone, thioxanthene, 2-oxothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthiophene Tons, 2-ethyl hydrazine, octadecyl hydrazine, 1,2-benzoquinone, 2,3-diphenylfluorene, azobisisobutyronitrile, benzammonium peroxide, peroxidation Propylbenzene, 2-mercaptobenzimidazole, 2-mercapto benzoxazole, 2-mercaptobenzoquinone, 2-(0-phenylphenyl)-4,5-di (metamethoxyphenyl)imidazolyl dimer, dioxin, 2-benzoicone, p,p'-bis(didecylamino)benzophenone, 4, 4'- Bis(diethylamino)benzophenone, 4,4'-dibenzobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, stupid formazan, benzoin, benzoin Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 18 1374155 benzoin butyl ether, phenyl ethyl ketone, 2, 2-diethoxyacetophenone, p-dimethylphenyl鲷, p-dimethylaminophenyl phenyl hydrazine, dichloro phenyl hydrazine, trichloro phenyl hydrazine, p-tert-butyl acetophenone, p-didecyl acetophenone, pair Tributyltrichlorobenzene, p-tert-butyldioxaacetophenone, α,α-dioxa-4-phenoxyacetophenone, thioxanthone, 2-nonylthioxanthone, 2- Isopropyl thioxanthone, diphenyl hydrazine, amyl 4-dimercaptophenyl benzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-anthracenyl)propane, p-methoxytriazine, 2, 4, 6-tris(tri-gasmethyl) are all tri-, 2-methyl-4,6-bis(trimethylsulfonyl)-tetra-, 2-[2-(5-decylfuran-2-yl)ethylene Base]-4,6-bis (trioxanyl) are all tris, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) are all three, 2 -[2-(4-Diethylamino-2-mercaptophenyl)vinyl]-4,6-bis(trichloroindenyl)-tetra-, 2-[2-(3,4-di Methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all-*, 2-(4-methoxyphenyl)-4,6-bis(trichloroindenyl)-three _, 2-(4-ethoxy stupid vinyl)-4,6-bis(trichloroindenyl)-tetra-, 2-(4-n-butoxyphenyl)-4,6-bis (three Chloromethyl) mesitri-, 2, 4-bis-trichloroindolyl-6-(3-bromo-4 -decyloxy)phenyl-tris-, 2,4-bis-tris-methyl- 6-(2-bromo-4-indolyl)phenyl-tris-, 2,4-bis-trisole Base-6-(3-di-4-pyrene-4-phenyl)phenylphenyl benzene, 2,4-di-trichloromethyl-6-(2-indol-4-yloxy)benzene The dilute phenyl groups are all three _ and so on. These photopolymerization initiators may be used singly or in combination of two or more. Among them, in terms of sensitivity, it is particularly preferable to use a lanthanide initiator. The content of the photopolymerization initiator (B) relative to the coloring photosensitive composition 19 1374155

The solid content is preferably from 0.5 to 30% by mass, more preferably from 1 to 2 (the range of H. By setting the content within the above range, sufficient properties, chemical resistance, and coating can be improved. The film forming ability is suppressed. <Colorant (C) &gt; As the coloring agent (C), an opacifier such as carbon black or titanium black may be used, and Cu, Fe, Mn, Cr, Co may be used. Various metal oxides of Ni, V, Zn, Se, Ca, Sr, Ba, Pd, Ag, Cd, I n, Sn, Sb, Hg, Pb, B i, and A1; composite oxides; metal sulfides It is a sulphate; or an inorganic pigment such as a metal carbonate. Among these coloring agents (C), a black pigment is preferably used. Examples of the black pigment include carbon black. As the carbon black, it can be used: tank black, furnace heat Known carbon black such as carbon black or lamp black, especially groove black, is suitable for use because it is excellent in hiding. Further, carbon black which is resin-based may be used. Specifically, carbon black and carbon are mentioned. A resin having a reactivity of a carboxyl group, a hydroxyl group or a carbonyl group on a black surface is mixed and heated at 380 degrees to obtain The resin-coated carbon black; or the monomer is dispersed in a water-organic solvent mixture or a water-surfactant mixture, and subjected to radical polymerization or base copolymerization in the presence of a polymerization initiator. Obtained resin-coated carbon black, etc. Since the conductivity of the tree-coated carbon black is lower than that of the carbon black not coated with the resin, it can be made in the case of a color filter such as a liquid crystal display. A display with low power consumption and low power consumption. As a coloring agent, it is also possible to add an organic pigment to the above inorganic pigment. The heat resistance is hard. Another Mg, Si, gold is used as black, and the optical coating is present. ~ Ethylene-based free-fat package can be used as 20 (S) 1374155 as an auxiliary pigment. The following effects can be obtained by appropriately selecting an organic pigment which exhibits a complementary color of an inorganic pigment. For example, carbon black exhibits a band. Red black. Therefore, by adding an organic pigment which exhibits red &lt;complementary color, that is, blue, as an auxiliary pigment in carbon black, the red color of carbon black can be eliminated [and the whole body exhibits a better black color. Inorganic The total amount of the material and the organic pigment is preferably from 10 to 80% by mass, more preferably from 20 to 60% by mass, more preferably from 20 to 40% by mass. As the above inorganic pigment and organic pigment A solution obtained by dispersing a pigment at a suitable concentration by using a dispersing agent can be used. For example, as an inorganic pigment, CFCAR (20% by weight) of a carbon dispersion liquid produced by Yuki Co., Ltd. can be used. The carbon dispersion Q Black (containing 243⁄4 of high-resistance carbon) and the titanium black dispersion cf Buck (containing 20% of titanium black pigment) manufactured by Yuki Co., Ltd. In addition, as the organic pigment, for example, The produced blue pigment dispersion liquid CFBlue (containing 2% by weight of blue pigment), the purple pigment dispersion liquid (including purple pigment) produced by Royal Chinese pigment, etc. In addition, as a dispersing agent, it is preferable to use: polyethylene An amine-based, urethane resin-based or acrylic resin-based polymer dispersant. The content of the coloring agent (C) is preferably from 10 to 70% by mass based on the solid content of the coloring photosensitive composition. By setting the content to 7% by mass or less, it is possible to suppress the photocuring failure, and by setting the content to 1% by mass or more, sufficient light blocking property can be obtained. Further, when the colored photosensitive composition of the present invention is used as a black matrix as described below, the concentration of the colorant (c) is preferably 每j) per 1 / m film thickness (〇pticai j) )ensity, 21 1374155

The optical density is adjusted to a value of 1.5 or more. If the 0D value per 1 β thick is 1.5 or more, when it is used for the black color of the liquid crystal display, sufficient contrast can be obtained. &lt;Solvent&gt; The colored photosensitive composition of the present invention preferably contains a solvent for use. Examples of the solvent include ethylene glycol monomethyl ether, alcohol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethyl ether monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol mono-n-propyl ether, di-n-butyl-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propanediol ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butylene dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propylene dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-(poly)alkylene glycol monoalkyl ether; ethylene glycol monoterpene ether Alkanediol monoalkane such as acid ester, ethylene diethyl ether acetate, diethylene glycol monoterpene ether acetate, diethylene glycol monoacetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate Ethyl acetates; diethylene glycol dimethyl ether, diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Other ethers; methyl ketone, cyclohexanone, 2-heptanone, 3 - ketones such as hydrazine; alkyl lactate such as 2-hydroxypropionic acid ethyl 2-hydroxypropionate; 2-hydroxy-2-mercaptopropyl ester, methyl 3-methoxyoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxylate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyethyl ester, 2-hydroxy-3-methylbutyric acid Ester, 3-methoxy-3-methoxybutyl 3-acetoxybutyrate, ethyl 3-indolyl-3-decyloxybutyrate, n-propyl acetate, isopropyl acetate , n-butyl acetate, ethyl m matrix matrix diluted ethylene glycol diol alcohol single mystery, ether, ether and other alcohol monoether B (poly) decyl alcohol ethyl ester, acid ethyl propionic acid, B, acetic acid iso 22 1374155 Butyl ester, n-amyl phthalate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, decyl pyruvate, pyruvic acid Other esters such as ethyl ester, n-propyl pyruvate, decyl acetate, ethyl acetate, 2-ethyloxybutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; N-fluorenyl Pyridoxamines such as pyrrolidone, N,N-dimethyldecylamine, hydrazine, hydrazine-dimethylacetamide, and the like. These solvents may be used singly or in combination of two or more.

The content of the solvent is preferably from 50 to 500 parts by mass based on 100 parts by mass of the solid content of the coloring photosensitive composition. &lt;Other components&gt; The colored photosensitive composition of the present invention may contain an additive as needed. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a surfactant, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing agent, a dispersing aid, a filler, and a adhesion promoter. , antioxidants, UV absorbers, anticoagulants, etc. &lt;Preparation method of coloring photosensitive composition&gt;

The colored photosensitive composition of the present invention can be obtained by mixing all of the above components with a stirrer. Further, it is also possible to filter using a filter to make the obtained mixture uniform. &lt;Manufacturing Method of Color Filter&gt; Hereinafter, a method of forming a color filter using the colored photosensitive composition of the present invention will be described. [Formation of black matrix] First, contact with a roller coater, a reverse coater, a bar coater, etc. 23 C S ) 1374155

A transfer type coating device or a non-contact type coating device such as a spin coater (a rotary coating machine or the like, which applies the present invention to a substrate. The substrate is used to have light transmissivity and then is applied) Coloring photosensitive group film. The drying method is not particularly limited, and for example, the method can be: (1) drying with a hot plate at a temperature of 80 to 120 ° C and C for 60 to 120 seconds; (2) to several days (3) a method of removing a solvent in a warm air heater or red for several tens of minutes to several hours. Then, the coating film is subjected to partial exposure by irradiating an active energy ray such as laser light through a negative mask. The amount is about 30 to 20 〇〇mj/cm 2 depending on the composition of the coloring photosensitive composition. Then, the film after exposure is formed into a desired shape by a developing solution. The development method is not particularly impregnated or sprayed. As a developing solution, an organic developing solution such as ethanolamine or triethanolamine or a water-soluble solution such as potassium, sodium carbonate, ammonia or a quaternary ammonium salt may be added, and the mixture may be baked at a temperature of about 2 Torr. When it is better to form the same by the above treatment , can form a predetermined pattern [by lithography forming a color filter using R, G, a sexual composition, for each color of the three primary colors and forming a top device), shower coloring The substrate of the sexual composition. The technique is dried to form a coating. It is preferably 90 to 1 放置 left at room temperature for several hours. The ultraviolet heater is placed in the external heater to emit ultraviolet light and excimer. The energy line to be irradiated is different, for example, it is preferably developed, and is defined by, for example, monoethanolamine, disodium hydroxide or hydroxide. After the pattern is made, the chess is fully exposed. Black matrix. The coloring agent is colored in the same manner as in the 24 1374155 mode in which the black matrix is formed, and coloring is sequentially formed on the substrate on which the black matrix is formed. [Formation of Color Filter by Inkjet Method] From the inkjet head, inks of respective colors of R, G, and B are ejected to respective regions divided by the black matrix formed as described above, and ink accumulated by heating or light is used. hardening. Thereby, a color filter can be formed. Floor. Way

[Examples] Hereinafter, examples of the invention will be described, but the invention is also set forth in the examples. &lt;Synthesis of Photopolymerizable Compound&gt; (Synthesis Example 1) In a 500 ml four-necked flask, 235 g (epoxy equivalent: 235) and four of the bisphenolphthalein type epoxy resin represented by the following chemical formula (8) were charged. Ammonium chloride 110 mg, 2,6-di-t-butyl-4-methylphenol 100 mg dilute acid 72. 0g, one side is blown into the air at a rate of 25 ml / min and heated at 90 to 100 ° C Dissolve. Then, slowly warm up the solution in a white turbid state, heat to 120 ° C, and completely dissolve it. Here the liquid gradually becomes transparent and viscous, and the stirring is continued in this state. Heating and stirring until the acid value reaches less than mgKOH/g. It takes 12 hours for the acid value to reach the target value. Then, to room temperature, a colorless transparent and solid biguanide type epoxy propylene I is obtained. Methyl and propyl j - in the form of a solution, 1. 0 cooling ί ester. 25 1374155

(8)

Then, 600 g of 3-methoxybutyl acetate was added to the above-mentioned bisphenolphthalein-type propylene oxide 307.0 g, and the mixture was dissolved in benzophenone tetracarboxylic dianhydride 80.5 g and tetraethyl benzene. The ammonium bromide is slowly heated and reacted at 11 0 to 1 15 °C. Thereafter, 38.0 g of 1,2, tetrahydrophthalic anhydride was mixed and reacted at 90 ° C to obtain an A-1. The disappearance of the acid anhydride group was confirmed by infrared spectroscopy. The weight average molecular weight of the substance A-1 as measured by GPC was 5,000. (Synthesis Example 2) As an epoxy compound having a biphenyl skeleton, Epikote YX4000H (manufactured by Japan Epoxy Resins, epoxy equivalent: 192) represented by the following (9), 400 g, and triphenylphosphine 4 g, 153 g of propylene and 600 g of 3-butoxy butyl acetate were mixed and allowed to react at 90 °C. Thereafter, 40 g of tetrahydrophthalic anhydride and 360 g of tetrahydrophthalic acid dianhydride were added as a polybasic acid anhydride, and further reacted to obtain a compound A-2 having a biphenyl skeleton. The disappearance of the acid anhydride group was confirmed by an external spectrum. The compound A-2 had a weight average molecular weight of 700% as determined by GPC. [Chemical 8] After the acid ester l, 1 g, 3, 6-chemical compound

Company company enoic acid - 100 phenyl this obtained by red amount 26 (S) 1374155

(Synthesis Example 3) 520 g of an NC-3000 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 188) represented by the following chemical formula (10) was used as an epoxy compound having a biphenyl skeleton, and 650 g of acetic acid 3 was used. Compound A-3 was synthesized in the same manner as in Synthesis Example 2 except for methoxybutyl ester. The weight average molecular weight of the compound A-3 as measured by GPC was 6,000. [Chemistry 9] ch2 a ch~ch2 I \ / ο ο CH2-CH'CH2 0 0

CH2lf (10) ch2-ch-ch2 I \ / 0 0 CH, (Synthesis Example 4) In addition to bisphenol A type epoxy resin, Epikote 828 (made by Japan Epoxy Resins Co., Ltd., epoxy equivalent: 190) 390 g as a ring Compound A-4 was synthesized in the same manner as in Synthesis Example 2 except for the oxygen compound. The weight average molecular weight of the compound A-4 as measured by GPC was 400 0. &lt;Examples and Comparative Examples&gt; With respect to the color-sensitive photosensitive compositions of the examples and the comparative examples, 150 g of the compounds A-1 to A-4 were used in the mass ratio shown in Table 1, and further, a dialer was used. And dipentaerythritol hexaacrylate 30g, ethyl ketone, 1-[9-ethyl-6-(2-mercaptophenyl)-9H-indazol-3-yl]-1-(0-acetamidine肟) (trade name: IRGACURE 0XE 02 , Ciba Specialty Chemicals 27 (S ) 1374155

Increasing from 10 mJ/cm2 to 180 mJ/cm in units of 5 mJ: development was carried out. &lt;Evaluation&gt; [CD sensitivity] In the above pattern forming method, when the line width of the black mask pattern (line) formed by the "Bias+1.0 to 20" m mask is 20 μmη + l /im, The exposure amount at this time is evaluated as the CD sensitivity. Since the coloring photosensitive composition in the present invention is a negative photoresist and the exposure amount is larger, CD (Critical Dimension) has a larger critical dimension. Usually, a target line for mass production The width is the mask line width + 1 to m. If the pattern can be formed with a lower exposure amount, the exposure can be shortened to increase the production line. [Thin line adhesion] The line width of the above line is 8 Forming a pattern, and observing the adhesion of the pattern by d observation. I will mark the pattern without peeling off. If there is a small amount of pattern peeling off, but there is no problem in practical application, it is recorded as [pattern linearity] by SEM observation, The linearity of the line pattern having an exposure amount of 65 mJ/cm 2 and a line width of 20 jtzm was evaluated. The line pattern edge was marked as "good", and the unevenness was marked as "bad". Contour] by SEM observation, right The outline shape of the pattern having an exposure amount of 65 mJ/cm 2 and a line width of 20 μm was evaluated. The pattern was a pattern before and after the post-baking treatment, and a substantially rectangular shape was recorded as "good, and Became, so) change 2 μ. Between SEM '◎, 〇. Developed into the side of the development 29 1374155

The result of the pattern defect and the time until the undercut is produced are good results. [Simple description of the diagram] None [Key component symbol description] None 31

Claims (1)

1374155 X. Patent application scope: 1. A coloring photosensitive composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), and a color former (C), characterized in that the photopolymerizable compound (A) contains a resin (A1) obtained by reacting an epoxy compound (a-fluorene) with a carboxylic acid compound (a-2) containing an ethylenically unsaturated group, and further reacting with a polybasic acid anhydride (a-3); The epoxy compound (a-fluorene) contains an epoxy compound having a biphenyl skeleton and an epoxy compound having a Cardo skeleton. 2. The colored photosensitive composition according to claim 1, wherein the resin (A1) contains: an epoxy compound having a biphenyl skeleton as the (a-Ι) component and the above ( a resin of the component (a-2), a resin (A1-1) obtained by reacting with the component (a-3); and an epoxy having an anthracene skeleton as the component (a-Ι) a resin obtained by reacting a compound with the above component (a-2) and further reacting with the above component (a-3) (A1-2)» 3. The coloring photosensitive composition as described in claim 1 The resin (A1) contains a reaction of an epoxy compound having a biphenyl skeleton as a component (a-Ι) and an epoxy compound having an anthracene skeleton with the above component (a-2). And a resin obtained by reacting with the above component (a-3) (Ab 3). The coloring photosensitive composition according to the first aspect of the invention, wherein the epoxy compound having a biphenyl skeleton is a compound represented by the following chemical formula (1), [Chemical 1] [In the formula (1), a plurality of R1 are each independently, and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and m is an average value, and represents a number of 0 to 10, η represents an integer of 1 to 4]. 5. The colored photosensitive composition according to claim 1, wherein the epoxy compound having a biphenyl skeleton is a compound represented by the following chemical formula (2), [Chemical 2] H3C rljU· In (2), m is an average value, indicating a number from 0 to 10. 6. The colored photosensitive composition of claim 4, wherein the value of m is less than 1. \7 C-C 'cv/c (2) (S ) 33 1374155 7. The colored photosensitive composition according to claim 1, wherein the epoxy compound having an anthracene skeleton is a compound represented by the following chemical formula (3). 8. The colored photosensitive composition according to claim 1, wherein the acid value of the resin (A1) is from 10 mgKOH/g to 150 mgKOH/g in terms of solid content. 9. The colored photosensitive composition according to claim 1, wherein the weight average molecular weight of the resin (A1) is 1,0 0 0 to 1 5, 00 0. 10. The colored photosensitive composition according to the first aspect of the invention, wherein the photopolymerizable compound (A) further contains a monomer containing an ethylenically unsaturated group. The colored photosensitive composition according to claim 1, wherein the coloring agent (C) is a black pigment. 34